Photographic material development method

ABSTRACT

A method of processing photographic materials wherein an imidazole compound is present during development to improve development characteristics, for example the speed of development, is disclosed.

United States Patent 1191 Field of Search 96/50, 66, 66.3, 109

Hara et a1. Apr. 30, 1974 PHOTOGRAPHIC MATERIAL [56] References Cited DEVELOPMENT METHOD UNITED STATES PATENTS [75] Inventors: Hikoharu Hara; Haruhiko Iwano; 2,453,346 11/1948 Russell 96/109 Katsumi Hosoya; Tadao Hatano; 3,086,863 4/1963 Hunt et a1 96/114 Tadao Yoo lsao 3,l26,282 3/1964 Hunt 96/59 Shimamura, all of Kanagawa, Japan Z1 f 2 eye e a [73] Assignee: Fuji Photo Film Co., Ltd., Minami, 3,576,633 4/1971 Henn et al. 96/66.5 Ashigara-shi, Kanagawa, Japan 3,649,281 3/1972 Iwano et aL 96/50 PT 3,698,900 10/1972 Johnson 96/109 Flledr y 1972 3,708,299 1/1973 Shimamura et al 96/50 R [21] Appl. No.: 257,208

Primary Examiner-Norman G. Torchln Related Apphcatlon Data Assistant Examiner-M. F. Kelley n in i f r- No. 7, n- 1970. Attorney, Agent, or Firm-Sughrue, Rothwell, Mion,

Zinn & Macpeak [30] Foreign Application Priority Data Jan. 24, 1969 Japan 44-5126 [57] ABSTRACT A method of processing photographic materials [52] US. Cl. 96/66.3, 96/50 PT, 9966/7292, wherein an imidazole compound is present during velopment to improve development characteristics, {2 603C 5/30 603C 5/26 G03: 5/50 for example the speed of development, is disclosed.

7 Claims, No Drawings CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation application of our earlier copending application Ser. No. 5,957, filed on Jan. 26, 1970, and claiming priority from Jan. 24, 1969 based on Japanese Patent application Ser. No. 5126/69, now abandoned.

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a silver halide photographic material and more particularly, it is concerned with a methodof processing a silver halide photographic lightsensitive material.

2. Prior Art In the development of a silver halide photographic material, it is desirable to promote the rate of development or to increase the speed of the photographic material. For these purposes, it is known to use amine compounds as development accelerators. Typical examples are alkylamines (as disclosed in U.S. Pat. No. 2,196,037), aralkylamines (as disclosed in U.S. Pat.

' Nos. 2,496,903; 2,515,147 and 2,541,889), phenoxyalkylamines (as disclosed in U.S. Pat. No. 2,482,546), heterocyclic alkylamines (as disclosed in U.S. Pat. No. 2,605,183), morpholine, piperidine, and the like (as disclosed in U.S. Pat. No. 2,304,025) and xylilenediamine (as disclosed in British Patent No. 1,086,618).

However, these amines generally have a bad odor. Furthermore, their concentrations in the processing solutions often cannot be held constant because of their volatility. Although the rate of development is accelerated by amines, the film speed does not increase correspondingly and rather an increase in fog and deterioration in the granularity of the developed silver are observed.

It is the principal object of this invention to provide a development accelerator capable of being used easily, of accelerating the rate of development and of increasing the effective speed with no fog increase nor deterioration of the silver image.

DESCRIPTION OF THE INVENTION For this object, the present invention provides a method of treating a photographic light-sensitive material which comprises developing a silver halide photographic light-sensitive material in the presence of an alkyl-substituted or hydroxyalkyl-substituted imidazole derivative represented by the following general formula,

wherein R R R and R each is selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyalkyl group and an alkenyl group and wherein at least one of R R R and R is selected from the group consisting of an alkyl group, a hydroxyalkyl group and an alkenyl group.

DETAILED DESCRIPTION OF THE INVENTION Illustrative compounds within the scope of the above formula and which can be used in the invention, are:

2-methylimidazole 4-methylimidazole 2,4-dimethylimidazole 2-ethyl-4-methylimidazole 2-amyl-imidazole l-isoamyl-2-methylimidazole 4,5-dimethylimidazole 2-ethylimidazole l-methylimidazole 2,4,5-trimethylimidazole 4-hydroxymethyl-5-methylimidazole 4-(2-hydroxyethyl)-5-methylimidazole 1-allyl-2-methylimidazole l-vinyl-2-methylimidazole The above compounds are known. Methods for their preparation are described in The Chemistry of Heterocyclic Compounds, Imidazole and Derivatives, Interscience Publishers, Inc., New York (1953). As is described in U.S. Pat. No. 3,126,282, imidazole can be added to the first step (black and white development) of a color reversal'processing for the films in which couplers are incorporated, but this compound is less effective in development acceleration than the alkylimidazole derivatives of the present invention.

The compounds of the present invention can be applied to silver halide photographic materials in general, as development accelerators in particular, for relatively low speed fine grain materials. Addition of the known development accelerators into a developer results in deterioration of graininess and resolution, which is particularly undesirable in materials used for high resolution purposes. On the contrary, use of the compounds of this invention is not accompanied by a comparable deterioration of the photographic image. In color reversal processing, the presence of the compounds of this invention in the black and white developer also increases the film speed or shortens the processing time. They act more effectively in increasing the rate of development, increasing the speed and image sharpness of a photographic image than the commonly used thiocyanates and alkylamines. Moreover, the compounds of the present invention are not accompanied by any increase in developer fog. The light-development can also be accelerated without deterioration of dot quality. The compounds of the present invention can be rapidly processed without raising the developing temperature, although with a combination of the imidazoles of the present invention and a temperature increase, a further reduction of processing time is also possible.

The developers to which the compound of the present invention can be effectively applied is the commonly used silver halide photographic developer, that is, aqueous solution containing one or more of hydroquinone, l-phenyl-3-pyrazolidone and N-methyl-paminophenol, to which antioxidants such as sodium sulfite or ascorbic acid, salts such as sodium sulfate, pI-I- adjusting compounds or pH-buffers such as boric acid, borax, sodium hydroxide, sodium carbonate or trisodium phosphate, development inhibitors such as potassium iodide or potassium bromide, and organic fog retarders such as 6-nitrobenzoimidazole or benzotriazole can be added. In some cases, aldehydes such as formaldehyde or glutaraldehyde can be added thereto. Besides being added to a developer, the compound of this invention can also be added to a bath prior to development or can be incorporated into a silver halide emulsion. ln the case of adding to a developer, the amount of the compound can generally range from 0.01 g. to 100 g. per 1000 ml. of the developer, preferably from 0.05 g. to 10 g./l. When the compound is added to a silver halide emulsion, a suitable amount can be from 0.01 g. to 50 g. per 1 mol. of silver halide and the addition can be carried out at any step in making the emulsion. Preferably, it is incorporated into the emulsion after the second ripening step and before the coating step. Furthermore, instead of incorporating the compounds of this invention directly into an emulsion layer, they can be added to an adjacent layer, such as a protective layer, after which it permeates through the emulsion layer. The compounds of the present invention can be applied to silver chloride, silver bromide, silver chlorobromide, silver iodide, silver iodobromide and silver chloroiodobromide emulsions. The emulsion can be sensitized chemically with an unstable sulfur compound, a gold compound or mixtures thereof. The emulsion can be spectrally sensitized with a cyanine dye or a merocyanine dye. The emulsion can be stabilized with a heterocyclic compound, such as 4-hydroxy- 6-methyl-l ,3,3a, 7-tetraxindene or l-phenyl-S- mercaptotetrazole. Furthermore, the emulsion can be hardened with a hardener such as formalin or mucochloric acid or can contain a surface active agent to facilitate coating.

The following examples are given to illustrate the invention further in detail, but without limiting it.

EXAMPLE 1 A fine grain positive film for cinematic use, on which a fine grain silver chlorobromide-gelatin emulsion had been coated, was subjected to development with a developer having the following composition at 27C.

Developer A Water 800 ml. N-Methyl-p-aminophenol sulfate 20 g. Sodium Sulfite I g. Hydroquinone g. Borax 2 g.

Water to make I000 ml.

EXAMPLE 2 A high speed film, comprising a support with a color sensitized silver iodobromide-gelatin emulsion coated thereon, was subjected to development at 20C. with a developer having the following composition.

Developer 8 Water 800 ml. l-Phenyl-3-pyrazolidone 0.2 g. Sodium Sulfite I00 g. Hydroquinone 5 g. Borax 2 g. Boric Acid 1 g. Potassium Bromide l g.

Water to make I000 ml.

The standard development time for the developer of the above formula was 8 minutes, but, when a compound of this invention, Z-methylimidazole, was added, the developing time was shortened as shown in Table A high resolution plate, comprising a support with an ultra-fine grain silver iodobromide gelatin emulsion coated thereon, was subjected to development at 20C. with a developer having the following composition.

Developer C Water 800 ml. l-Phenyl-Z-pyrazolidone 0.5 g. Sodium Sulfite 50 g. Hydroquinone 12 g. Sodium Carbonate Monohydrate g. Potassium Bromide 2.0 g. Benzotriazole 0.2 g.

Water to make 1000 ml.

The standard development time for the developer of the above formula was 6 minutes, but when a compound of this invention, 2-methylimidazole, was added, the developing time was shortened as shown in Table 3 below. Development in 6 minutes with addition of the compound of the invention gave the high speed as s wn in Tabl .b Q

TABLE 1 Developer A Amount Development in 4 Min. Developing Time Required for g./l. Relative Fog Gamma Obtaining a Relative Sensitivity of Sensitivity Control 0 I00 0.04 1.35 4 min. with Z-Methylimidazole l 220 0.04 1.35 2 min. with Z-Methylimidazole 4 430 0.05 L40 l min.

ing composition.

TABLE 3 Amount Developmentin4Minl m w R N 7 A N -BE/l' Relative Fog Gamma r l 7 Developing Time Required for Obtaining C Sensitivity BJSQ EEXESEE EE LY 9EQ W.

Control 0 100 -0.04 3.24 m' n. My with 2-Methvlimidazole 1 I80 0.04 3 8 0 i 3 min.

EXAMPLE 4 EXAMPLE 5 A fine grain positive film for cinematic use comprising a support with a fine grain silver chlorobromidegelatin emulsion coated thereon, was subjected to development at 24C. with a developer having the follow- Water to make I000 ml.

"The standard development time for the developer of the above formula was 5 minutes, but, when l X mol./l. of a compound of the invention was added, the developing time was shortened as shown in Table 4 below.

A microfilm, comprising a support with a fine grain silver chlorobromide-gelatin emulsion coated thereon,

I was subjected to development at C. with a developer having the following composition.

Water to make 1000 ml.

The standard development time for a developer of the above formula was 4 minutes, but, when a compound of this invention, 2-methylimidazole, was added, the developing time was shortened as shown in Table 5 below. Development in 4 minutes with the addition of a compound of this invention gave a high speed as with 4-Allyl-2-methylimidazole TABLE 5 Amount Development in4Min.

Developing Time Required for Obtaining g./l. I Relative FogGamma DeyeloperE Sensitivity a Relative Sensitivity of I 7 Control o foo T 0.19 4.00 4 min. with Z-Methylimidazole l 0.]9 4.l0 2 min. with Z-Melhylimidazole 4 0.20 4.15

l min.

EXAMPLE 6 A high speed direct X ray film, comprising a support with a silver iodobromide-gelatin emulsion coated therb. a yellow filter layer;

0. a green-sensitive silver halide-gelatin emulsion layer containing a magenta color coupler forming a magenta dye;

d. a red-sensitive silver halide-gelatin emulsion layer containing a cyan color coupler forming a cyan dye;

e. a film support; was subjected to development at 20C. for 15 minutes a i alh f w s.d ve r',

eon, was subjected to a high temperature rapid development at 35C. with Developer C of Example 3. With Developer C, 100 seconds was ordinarily required for d development, but, when a compound of this invention was added, the developing time was shortened as shown in Table 6 below TABLE 6 Developer C Amount Added Developing Time containing g./l. (moi/l.)

Control 0 100 see. with Z-Methylimidazole 2.] (2.5 X 10 55 see. with 2-Methylimidazole 4.2 (5.0 X 10 45 see. with 2-Methylimidazole 2.4 (2.5 X 10 45 see. with 2,4-Dimethylimidazole 2.4 (2.5 X I04) 45 sec. with 2,4-Dimethylimidazole 4.8 (5.0 X 10-) 40 sec.

EXAMPLE 7 A lithographic film for photomechanical use, comprising a support and a silver chlorobromide-gelatin emulsion coated thereon, was subjected to development at 20C. with a developer having the following composition.

Developer F Water Sodium Sulfite Paraformaldehyde Potassium Bisulfite Boric Acid Hydroquinone Potassium Bromide Water to make 1000 ml.

The standard development time for the developer of the above formula was 2 minutes, but when a compound of this invention, 2-methylimidazole, was added, the developing time was shortened as shown in Table 7 below, without lowering the net point quality.

TABLE 7 Developer F Amount Added Developing Time Control 0 2 min. with 2-Methylimidazole l l min. sec. with Z-Methylimidazole 2 l min.

EXAMPLE 8 A color photographic material, comprising substantially:

a. a blue-sensitive silver halide-gelatin emulsion layer containing a yellow color coupler forming a yellow dye by reaction with an oxidized developing agent;

Developer G Water 800 ml. N-Methyl-p-aminophenol Sulfate 3.0 g. Sodium Sulfite 50 g. Hydroquinone 6.0 g. Sodium Carbonate Monohydrate 42 g. Potassium Bromide 3.0 g.

Water to make I000 ml.

The film was immersed in a solution of chrome alum for 3 minutes, then both sides were irradiated with white light and developed for 15 minutes with a color forming developer having the following composition:

Color Fonning Developer Water Benzyl Alcohol Sodium Sulfite Trisodium Phosphate l2-Hydrate Potassium Bromide Sodium Hydroxide Citrazinic Acid 4-Amino-N-ethyl-N-(beta.methanesulfonamide ethylym-toluidine Sesquisulfate Monohydrate Water to make 1000 ml.

TABLE 8 Color Forming Developer Amount Added Developing Time moL/l.)

Control 0 15 min with Z-Methylimidazole 0.82 9 min. with 2,4-Dimethylimidazole 0.96 9 min. with l-Mcthylimidazole 0.82 8 min. with l-Allyl-2-Mcthylimidazolc 1.22 7 min. with Potassium Thiocyanatc 0.97 12 min.

m M 9 M..- w 1P0 EXAMPLE 9 "w k c C I F o A reversal color film whose couplers are lncorpoom ommg Hemp" rated in the developers, comprising a support of cellu- Water 800 ml. lose acetate film and a red-sensitive silver iodobro- 2-Aminc-5-dlethylamlnotoluene mide-gelatin emuls1on,a green-sensitive silver rodobro- Hydrochloride 0.6 g. mide-gelatin emulsion, a blue light absorbing yellow filcagbwam Mnhydrate 8- ter layer consisting of colloidal silver and a blue- 5% 1% 5 sensitive silver iodobromide-gelatin emulsion coated soluligml thereon in the order shown, was developed at 24C. for I O lg gig g g l 2 g five minutes with a black and white developer having Sodium Hydroxide 210 g:

- 'Monobenzyl-p-aminophenol the following composition. Hydrochloride 0.2

- Water to make I000 ml.

Developer H ','ljg H 15 e thus treated film was then washed with water for water 800 five minutes, desilvered for two minutes with a bleachgtxzg imz Sulfate 3- smg solution containing 100 g. of potassium ferricyanide Hydroquinone 8.0 E and l0 g. of potassium bromide per 1 liter and fixed for gozilum Caabonatje Monohydrate 5%.(5) g 2 minutes wlth a solution of sodium thiosulfate. The

0 55mm roml e g water to make 000 mL characteristic values of the film subjected to cyan reversal development are shown in Table 9 below.

W TABLE 9 Text No. Amount Added 7 Qhagagterigg'g Valggs g./l. (0.01 m./l.) Relative Maximum Sensitivity Density Values .A; Ce ral j ,A 0 V 100 3.32 B Z-Methylimidazole 0.82 270 3.25 C l-Methylimidazole 0.82 320 3.13 D l-Allyl-2-methylimidazole 1.22 560 3 .03

This developer was divided into 4 parts with one to 40 7 h EXAMPLE l0 2 be used as a control and compounds of this invention Z-Methylimidazole of the invention in the form of were added to the remaming three.

aqueous solution was added to a silver iodobromider gelatin emulsion containing 3.0 mol. percent of silver iodide and coated onto a film base, followed by drying.

8) ztii ei ylimidazoie 0.22 gJl (1:01 moL/l.) The test film was developed at 24C. for 5 minutes with C) l-Methylimidazole 0.82 g./l. 0,01 moL/l.) o) l-Allyl-Z-methylimidazole 1.22 g.ll. (0.01 mol.ll.) Developer D of Example 4 The resumng photograph characteristic values are shown in Table 10 below.

- TABLE i0 Emulsion Addition Amount Qharagteriggjg. Values gJl. mole silver Relative Fog Gamma halide Sensitivity Control 0 0.05 0.85 with 2-Methylimidazole 2 0.06 0.90 with 2-Methylimidazole 8 0.07 0.82

Then the film was washed witfiwater *rori'w'o min- What is claimed is: utes, 1. A process for accelerating the development of an subjected to reversal exposure by red light from the exposed gelatino-silver halide photographic lightback of the film and treated with a cyan color forming sensitive material, which comprises:

developer having the following composition at 24C. 65 treating Said p g aphi rial with a member f r fiv mi t selected from the group consisting of a pre-bath for 1 1 development and a developer, said pre-bath comprising a conventional pre-bath for development and an imidazole derivative, and said developer comprising a conventional photographic developer and an imidazole derivative, said imidazole derivative represented by the following formula:

wherein R R R and R each represent a member selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyalkyl group, and an alkenyl group, and wherein at least one of said R R R and R is a member selected from the group consisting of an alkyl group, a hydroxyalkyl group, and an alkenyl Q Pa a .7 .7 w V m V methylimidazole, 4,5-dimethylimidazole, 2,4,5- trimethylimidazole, 4-hydroxymethyl-5- methylimidazole, 4-( Z-hydroxyethyl )-5- methylimidazole, and l-vinyl-2-methylimidazole.

6. The process of claim 1, wherein said compound is present in an amount of from 0.01 to grams per liter of developer.

7. The process of claim 6, wherein said amount ranges from 0.05 to 10.0 grams per liter of developer. 

2. The process of claim 1, wherein said compound is a member selected from the group consisting of 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-ethylimidazole, and 1-allyl-2-methylimidazole.
 3. The process of claim 1, wherein said compound is 1-methylimidazole.
 4. The process of claim 1, wherein said compound is 2-methylimidazole.
 5. The process of claim 1, wherein said compound is a member selected from the group consisting of 4-methylimidazole, 2-amylimidazole, 1-isoamyl-2-methylimidazole, 4,5-dimethylimidazole, 2,4,5-trimethylimidazole, 4-hydroxymethyl-5-methylimidazole, 4-(2-hydroxyethyl)-5-methylimidazole, and 1-vinyl-2-methylimidazole.
 6. The process of claim 1, wherein said compound is present in an amount of from 0.01 to 100 grams per liter of developer.
 7. The process of claim 6, wherein said amount ranges from 0.05 to 10.0 grams per liter of developer. 